CN117509629A - Edge fluorinated nano graphene material and preparation method and application thereof - Google Patents
Edge fluorinated nano graphene material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117509629A CN117509629A CN202311591092.0A CN202311591092A CN117509629A CN 117509629 A CN117509629 A CN 117509629A CN 202311591092 A CN202311591092 A CN 202311591092A CN 117509629 A CN117509629 A CN 117509629A
- Authority
- CN
- China
- Prior art keywords
- edge
- nano graphene
- fluorinated
- graphene material
- fluorinated nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 44
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 11
- 230000005669 field effect Effects 0.000 claims abstract description 4
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 4
- 238000012984 biological imaging Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 104
- 239000000203 mixture Substances 0.000 claims description 34
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001925 cycloalkenes Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000007547 defect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- UHDDEIOYXFXNNJ-UHFFFAOYSA-N (3,4,5-trifluorophenyl)boronic acid Chemical compound OB(O)C1=CC(F)=C(F)C(F)=C1 UHDDEIOYXFXNNJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000004007 reversed phase HPLC Methods 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000003779 heat-resistant material Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 239000003879 lubricant additive Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004776 molecular orbital Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005556 structure-activity relationship Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002424 x-ray crystallography Methods 0.000 description 2
- PHBVXHIVWULVNF-UHFFFAOYSA-N (4-fluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(F)C=C1 PHBVXHIVWULVNF-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 231100000263 cytotoxicity test Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an edge fluorinated nano graphene material and a preparation method and application thereof. The edge fluorinated nano graphene material is prepared from a new synthesis strategy of fluorine atom preinstallation and combination from bottom to top by using decachlorocentered graphene as a starting material through a Suzuki-Miyaura coupling reaction and a Scholl reaction; the preparation method successfully solves the problem that the severe reactivity of the fluorination reaction causes no selectivity, not only well maintains the pi conjugated system of the nano graphene, but also realizes the precise multifluorination and even perfluorination of the edge of the nano graphene. The edge fluorinated nano graphene material, in particular to the edge perfluorinated nano graphene, has high electron affinity, low molecular orbital energy level, high electron mobility, good solubility, thermal stability, conductivity and biocompatibility, and has potential application in the fields of organic light emitting diodes, organic photovoltaic cells, organic field effect transistors, biological imaging/biomedicine and the like.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to an edge fluorinated nano graphene material and a preparation method and application thereof.
Background
Fluorinated nanographene materials are nanocarbon materials that introduce fluorine atoms into the interior or edges of graphene sheets between 1 and 100nm in size. The physical, chemical and photoelectric properties of the fluorinated nano graphene are greatly improved compared with those of the fluorinated nano graphene before fluorination due to the introduction of fluorine atoms, so that the fluorinated nano graphene has wide application prospects in the fields of organic semiconductors, electrode materials, high-stability materials, novel biomedical materials and the like.
The traditional method for preparing fluorinated nano-graphene materials is a direct fluorination method. Due to the severe reactivity of the fluorination reaction, the pi conjugated system of the product prepared by the method is often destroyed, and the original properties of the graphene in the aspects of electric conduction, heat conduction, photophysics, electrochemistry and the like are not possessed. In addition, the direct fluorination method has no regioselectivity, and the position and the quantity of the fluorination reaction are not controllable, so that the prepared product is complex in type, a single product is difficult to obtain, the structure-activity relationship of the product cannot be deeply studied, and the development of the application of the product is greatly limited.
Disclosure of Invention
In order to solve the problems, the invention gets rid of the limitation of the traditional fluorination method, and provides a novel preparation method of the edge polyfluoro or perfluorinated nano graphene material with a definite structure through a new synthesis strategy of fluorine atom preinstallation and combination from bottom to top. The invention realizes that the fluorination is only carried out at the edge of the nano graphene. The product with a definite structure is obtained through controllable fluorination quantity and position while the pi conjugated system of the graphene kernel is completely reserved, and the properties of the product and the application of the product in the fields of organic semiconductors, biomedicine and the like are explored.
The invention adopts the following technical scheme:
the edge fluorinated nano graphene material takes nano graphene as an inner core, hydrogen atoms at the edge of the inner core are replaced by a certain number of fluorine atoms, and the replacement number of the fluorine atoms is 10-30; the chemical structural formula of the edge fluorinated nano graphene material is as follows:
wherein R is 1 And R is 2 When the fluorine atoms and the hydrogen atoms are respectively adopted, the molecular formula of the edge fluorinated nano graphene material is C 80 H 20 F 10 ；R 1 And R is 2 When the fluorine atoms are hydrogen atoms and fluorine atoms respectively, the molecular formula of the edge fluorinated nano graphene material is C 80 H 10 F 20 ；
When R is 1 And R is 2 When the two are fluorine atoms, the bonding modes of the edge fluorinated nano graphene material are respectively complete cyclization and incomplete cyclization, wherein when the two are completely cyclized, a bond is formed at a dotted line, and the molecular formula of the edge fluorinated nano graphene material is C 80 F 30 The method comprises the steps of carrying out a first treatment on the surface of the When the cyclisation is incomplete, no bond is formed at the dotted line, and the molecular formula of the edge fluorinated nano graphene material is C 80 H 6 F 30 。
Preferably, the inner core is all six-membered rings or contains defects other than six-membered rings, which are five-, seven-or eight-membered rings; when all the cores are six-membered rings, the whole space structure of the inner core is a plane; when the core contains non-six-membered ring defects, the whole space structure of the core is bent, and the structural fragment comprises any one of the following components:
preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, the edges replace 10 fluorine atoms altogether, R 1 Is a fluorine atom, R 2 Is a hydrogen atom, namely the molecular formula of the edge fluorinated nano graphene material is C 80 H 20 F 10 The chemical structural formula is as follows:
preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, 30 fluorine atoms are substituted at the edge, and the benzene substituent is completely cyclized, R 1 And R is 2 Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C 80 F 30 The chemical structural formula is as follows:
preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, the edge is substituted with 30 fluorine atoms and the benzene substituent is incompletely cyclized, R 1 And R is 2 Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C 80 H 6 F 30 The chemical structural formula is as follows:
the preparation method of the edge fluorinated nano graphene material specifically comprises the following steps:
s1, realizing the coupling of ten-weight Suzuki-Miyaura under the action of a palladium catalyst by using decachlorocycloalkene and 4-fluorobenzeneboronic acid to obtain ten (4-fluorophenyl) cycloalkene;
s2, carrying out intramolecular dehydrocyclization reaction on the ten (4-fluorophenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through RP-HPLC to obtain the edge-decafluoro-substituted edge-fluorinated nano graphene material C 80 H 20 F 10 。
The preparation method of the edge fluorinated nano graphene material specifically comprises the following steps:
s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;
s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through RP-HPLC to obtain the edge perfluorinated completely cyclized edge fluorinated nano graphene material C 80 F 30 。
The preparation method of the edge fluorinated nano graphene material specifically comprises the following steps:
s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;
s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through silica gel column chromatography to obtain the edge polyfluoro-substituted incompletely cyclized edge fluorinated nano graphene material C 80 H 6 F 30 。
Preferably, the alkali adopted by the Suzuki-Miyaura coupling reaction is potassium phosphate; the organic solvent adopted in the Suzuki-Miyaura coupling reaction is toluene; the oxidant used in the Scholl reaction is 2, 3-dichloro-5, 6-dicyano-p-benzoquinone; the organic acid used in the Scholl reaction is trifluoromethanesulfonic acid; the organic solvent used in the Scholl reaction is methylene dichloride.
An application of an edge fluorinated nano graphene material as an n-type semiconductor applied to an organic field effect transistor, an organic light emitting diode and an organic photovoltaic cell; the edge fluorinated nano graphene material is used as a heat-resistant material and is suitable for a lubricant additive in high-temperature, high-speed and high-pressure environments; the edge fluorinated nano graphene material is suitable for biological imaging and biomedicine as a biological friendly material.
After the technical scheme is adopted, compared with the background technology, the invention has the following advantages:
1. according to the invention, edge polyfluoro and even perfluorinated of the nano graphene are realized, pi conjugated structure and property of the inner core of the nano graphene are completely reserved, and a new strategy and thought are provided for accurately synthesizing more peripheral polyfluoro substituted nano graphene.
2. The product of the invention can be separated and purified by conventional means, and can be clearly and structurally characterized by means of high-resolution mass spectrum, nuclear magnetic resonance hydrogen spectrum, carbon spectrum, fluorine spectrum, X-ray single crystal diffraction and the like, so that the structure-activity relationship can be deeply studied by combining the optical, electrical and other properties of the product.
3. The material of the invention has a special chiral saddle-shaped topological structure, and reduces intermolecular acting force due to strong electronegativity of fluorine atoms and substitution of edge fluorine atoms, compared with an unmodified saddle-shaped topological structure C 80 H 30 ，C 80 F 30 And C 80 H 6 F 30 And the like, have better solubility, higher fluorescence quantum yield and lower highest occupied orbital (HOMO) energy level and lowest unoccupied orbital (LUMO) energy level. The fluorinated nano graphene material has good electron transmission performance (figure 8) due to the complete retention of pi conjugated structure and high electron affinity due to edge fluorination, so that the fluorinated nano graphene material can be used as a potential electron acceptor material for devices such as an organic light emitting diode OFET, an organic field effect transistor OLED or an organic photovoltaic cell OPV.
4. According to the invention, with the increase of fluorine content, the high bond energy of the C-F bond can obviously improve the thermal stability of the nano graphene. Wherein the thermogravimetric analysis of the edge perfluorinated product showed a sharp weight loss between 600 and 700 ℃ with a maximum slope of 635 ℃. The dissociation temperature is improved by about 90 ℃ compared with the nano graphene before fluorination. In addition, the dissociation temperature of the decafluoronated product is also significantly increased compared to that before fluorination (fig. 9). The nano graphene material with the fluorinated edges has higher thermal stability, and can be used as a potential heat-resistant material in the fields of catalysis, lubrication and semiconductors. They can withstand high temperature, corrosive and oxidative environments, thereby extending the useful life and reliability of the device or equipment.
5. HeLa cells were incubated with two poly-fluorinated nanographene dimethyl sulfoxide (DMSO) solutions prepared in accordance with the present invention for 24 hours or 48 hours at 37℃ (FIG. 10). The results show that the decafluorinated and perfluorinated nano-graphenes have almost no toxicity at the temperature of up to 200 mu M, which indicates that the edge fluorinated nano-graphenes have good in-vitro biocompatibility and can be used in the fields of biological monitoring and biological medicine.
Drawings
FIG. 1 is a high resolution mass spectrum of edge decafluorinated graphene nanomaterial prepared in accordance with example one of the present invention;
FIG. 2 shows edge decafluorinated nanographene materials prepared according to example I of the present invention 1 HNMR spectrogram;
FIG. 3 is a high resolution mass spectrum of edge perfluorinated nanographene materials prepared according to example two of the invention;
FIG. 4 shows edge perfluorinated nanographene materials prepared according to example II of the invention 19 FNMR map;
FIG. 5 is a schematic illustration of an edge perfluorinated nanographene material prepared in accordance with example II of the present invention 13 C{ 19 F } NMR chart;
FIG. 6 is a high resolution mass spectrum of edge polyfluorinated graphene prepared in example III of the present invention;
FIG. 7 is a schematic illustration of edge polyfluorinated nanographene material prepared according to example III of the invention 13 C{ 19 F } NMR chart;
FIG. 8 is a graph comparing electron mobility of edge perfluorinated nanographene materials and PCBM prepared in accordance with example two of the present invention;
FIG. 9 is a thermogravimetric analysis curve of edge perfluorinated nanographene materials prepared according to example two of the invention;
FIG. 10 shows the cytotoxicity test results of edge polyfluorinated graphene nano-materials prepared according to the first and second embodiments of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The test methods described in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
See fig. 1 to 10.
Example 1
Edge decafluorinated nanographene material of this example (C 80 H 20 F 10 ) The structural formula is as follows:
the synthetic route is as follows:
(1) Decocyclotriene (119 mg,0.2 mmol), 4-fluorophenyl boric acid (839 mg,6 mmol), pd (PPh) 3 ) 4 (277 mg,0.2 mol) and K 3 PO 4 (1.48 g,7 mmol) was charged to a 50mL two-necked round bottom flask and charged with N 2 Three times. Then 10mL of degassed toluene, 10mL of degassed H are added to the mixture 2 O and 5mL of degassed 1, 4-dioxane. The mixture was then stirred at 100℃for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with Dichloromethane (DCM) and washed 3 times with water. The DCM layer was collected and concentrated, and the crude product was purified by silica gel column chromatography eluting with hexane: dichloromethane (v: v) =2:1 to give deca (4-fluorobenzene) based cycloalkene as a yellow powder (yield 61%). 1 H NMR(400MHz,CDCl 3 ,298K)δ6.51(dd,J(F,H)＝12Hz,20H),6.30(t,J(F,H)＝16Hz,20H). 13 C NMR(100MHz,CDCl 3 ,298K)δ162.16-159.71(d,J(C,F)＝245Hz),142.21,135.00(d,J(C,F)＝4Hz),133.12(d,J(C,F)＝8Hz),132.06,127.77,113.56(d,J(C,F)＝21Hz).HRMS(Maldi-TOF-MS)m/z calcd for C 80 H 40 F 10 [M] - :1189.289,found:1189.873.
(2) Edge decafluorinated nanostonesGraphene material (C) 80 H 20 F 10 ) Is synthesized by the following steps:
ten (4-fluorobenzene) based Cycloalkene (119 mg,0.1 mmol), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ, 681mg,3 mmol) was added to a 25mL two-necked flask and charged with N 2 Three times. To the mixture was then added 10mL of dried Dichloromethane (DCM) and 1.5mL of trifluoromethanesulfonic acid (TfOH). The mixture was then stirred at room temperature for 30 minutes. Then 10mL of saturated NaHCO was added to the mixture 3 The solution was used to quench the reaction. The mixture was extracted with DCM and washed 3 times with water. The organic phase was collected and evaporated, and the crude product was then separated by silica gel column chromatography eluting with hexane: dichloromethane=2:1 (v: v) to obtain a mixture of edge decafluorinated nanographene and some by-products of incomplete dehydrocyclization (determined as C by MS 80 H 22 F 10 And C 80 H 24 F 10 ). The mixture was further purified by RP-HPLC to give 9.6% yield of edge decafluorinated nanographene material (C 80 H 20 F 10 )。 1 H NMR(400MHz,1,1,2,2-tetrachloroethane-d 2 ,363K)δ8.09-8.07(d,J(F,H)＝8Hz,10H),7.30-7.28(d,J(F,H)＝8Hz,10H).HRMS(Maldi-TOF-MS)m/zcalcd for C 80 H 20 F 10 [M] - :1170.140,found:1170.132.
Table 1 example one prepared edge decafluorinated nanographene material (C 80 H 20 F 10 ) X-ray crystallography data sheet of (2)
Example two
The edge perfluorinated nanographene material (C 80 F 30 ) The structural formula is as follows:
the synthetic route is as follows:
(1) Decocyclotriene (119 mg,0.2 mmol), 3,4, 5-trifluorophenylboronic acid (1.06 g,6 mmol), pd (PPh) 3 ) 4 (277 mg,0.2 mol) and K 3 PO 4 (1.48 g,7 mmol) was charged to a 50mL two-necked round bottom flask and charged with N 2 Three times. Then 10mL of degassed toluene, 10mL of degassed H are added to the mixture 2 O and 5mL of degassed 1, 4-dioxane. The mixture was then stirred at 100℃for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with Dichloromethane (DCM) and washed 3 times with water. The DCM layer was collected and concentrated, and the crude product was purified by silica gel column chromatography eluting with hexane: dichloromethane (v: v) =2:1 to give deca (3, 4, 5-fluorobenzene) based cycloalkene as a yellow powder (yield 58%). 1 H NMR(400MHz,CD 2 Cl 2 ,298K)δ6.43(t,J(F,H)＝12Hz,20H). 13 C NMR(100MHz,CD 2 Cl 2 ,298K)δ151.63-149.18(d,J(C,F)＝245Hz),140.45,134.14,133.04,127.18,116.26(d,J(C,F)＝6Hz),116.11(d,J(C,F)＝6Hz).HRMS(Maldi-TOF-MS)m/z calcd for C 80 H 20 F 30 [M] - :1549.100,found:1549.414.
(2) Edge perfluorinated nanographene materials (C 80 F 30 ) Is synthesized by the following steps:
ten (3, 4, 5-trifluorobenzene) base Cycloalkene (133 mg,0.086 mmol), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ, 780.9mg,3.44 mmol) was added to a 25mL two-necked flask and charged with N 2 Three times. To the mixture was then added 10mL of dried Dichloromethane (DCM) and 3mL of trifluoromethanesulfonic acid (TfOH). The mixture was then stirred at room temperature for 90 minutes. Then 10mL of saturated NaHCO was added to the mixture 3 The solution was used to quench the reaction. The mixture was extracted with DCM and washed with waterWashing 3 times. The organic phase was collected and evaporated, and the crude product was then separated by silica gel column chromatography eluting with hexane: dichloromethane=40:1 (v: v) to obtain a mixture of edge perfluorinated nanographene material and some by-products of incomplete dehydrocyclization (two other products were determined to be C by MS 80 H 2 F 30 And C 80 H 4 F 30 ). The mixture was further purified by RP-HPLC to give edge perfluorinated C in 6% yield 80 F 30 A nano graphene material. 13 C{ 19 F}NMR(150MHz,CD 2 Cl 4 ,298K)δ175.57,151.57,151.54,150.18,149.72,149.66,149.64,149.30,149.24,149.14,149.04,148.83,148.78,147.97,147.93,147.87,146.91,140.83,140.71,140.57,140.45,140.28,140.03,139.87,139.78,138.67,138.61,137.00,136.98,136.49,136.44,133.99,133.64,133.40,132.72,132.38,132.31,131.64,131.51,131.33,131.31,131.19,131.05,130.91,130.79,130.73,130.42,130.33,130.24,130.20,129.80,129.71,129.61,129.28,129.18,129.14,128.82,128.76,127.80,116.32,116.25,113.47,113.45,113.36,113.02,112.92,112.36,112.15,112.09,111.92,111.84,111.64,111.29,111.21,111.18,110.76,110.65,110.59,110.21,109.98. 19 F NMR(565MHz,CD 2 Cl 4 ,298K)δ-121.29(d,J(F,F)＝24Hz,1F),-121.68(d,J(F,F)＝18Hz,1F),-121.85(t,J(F,F)＝24Hz,1F),-121.96(t,J(F,F)＝30Hz,1F),-122.15(t,J(F,F)＝30Hz,1F),-122.77(t,J(F,F)＝30Hz,1F),-123.04(t,J(F,F)＝30Hz,1F),-123.04(t,J(F,F)＝30Hz,1F),-126.04(t,J(F,F)＝30Hz,1F),-126.90(dd,J(F,F)＝60Hz,1F),-127.40(t,J(F,F)＝30Hz,1F),-127.45(t,J(F,F)＝30Hz,1F),-127.86(dd,J(F,F)＝60Hz,1F),-129.13(dd,J(F,F)＝60Hz,1F),-129.44(dd,J(F,F)＝60Hz,1F),-129.63(t,J(F,F)＝24Hz,1F),-129.97(d,J(F,F)＝6Hz,1F),-130.19(dd,J(F,F)＝48Hz,1F),-130.34(dd,J(F,F)＝48Hz,1F),-134.31(t,J(F,F)＝42Hz,1F),-153.76(t,J(F,F)＝60Hz,1F),-153.87(t,J(F,F)＝60Hz,1F),-153.92(t,J(F,F)＝60Hz,1F),-154.60(t,J(F,F)＝60Hz,1F),-155.08(t,J(F,F)＝60Hz,1F),-155.67(t,J(F,F)＝42Hz,2F),-155.97(t,J(F,F)＝48Hz,1F),-155.74(m,J(F,F)＝78Hz,2F).HRMS(Maldi-TOF-MS)m/z calcd for C 80 F 30 [M] - :1529.952,found:1529.952.
Table 2 edge-perfluorinated nanographene (C) prepared in example two 80 F 30 ) X-ray crystallography data table of (2);
example III
Edge polyfluorinated nanographene material of this example (C 80 H 6 F 30 ) The structural formula is as follows:
the synthetic route is as follows:
(1) Decocyclotriene (119 mg,0.2 mmol), 3,4, 5-trifluorophenylboronic acid (1.06 g,6 mmol), pd (PPh) 3 ) 4 (277 mg,0.2 mol) and K 3 PO 4 (1.48 g,7 mmol) was charged to a 50mL two-necked round bottom flask and charged with N 2 Three times. Then 10mL of degassed toluene, 10mL of degassed H are added to the mixture 2 O and 5mL of degassed 1, 4-dioxane. The mixture was then stirred at 100℃for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with Dichloromethane (DCM) and washed 3 times with water. The DCM layer was collected and concentrated, and the crude product was purified by silica gel column chromatography eluting with hexane: dichloromethane (v: v) =2:1 to give deca (3, 4, 5-fluorobenzene) based cycloalkene as a yellow powder (yield 58%). 1 H NMR(400MHz,CD 2 Cl 2 ,298K)δ6.43(t,J(F,H)＝12Hz,20H). 13 C NMR(100MHz,CD 2 Cl 2 ,298K)δ151.63-149.18(d,J(C,F)＝245Hz),140.45,134.14,133.04,127.18,116.26(d,J(C,F)＝6Hz),116.11(d,J(C,F)＝6Hz).HRMS(Maldi-TOF-MS)m/z calcd for C 80 H 20 F 30 [M] - :1549.100,found:1549.414.
(2) Polyfluorinated nanographene materials (C 80 H 6 F 30 ) Is synthesized by the following steps:
ten (3, 4, 5-trifluorobenzene) base Cycloalkene (133 mg,0.086 mmol), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ, 780.9mg,3.44 mmol) was added to a 25mL two-necked flask and charged with N 2 Three times. To the mixture was then added 10mL of dried Dichloromethane (DCM) and 3mL of trifluoromethanesulfonic acid (TfOH). The mixture was then stirred at room temperature for 90 minutes. Then 10mL of saturated NaHCO was added to the mixture 3 The solution was used to quench the reaction. The mixture was extracted with DCM and washed 3 times with water. The organic phase was collected and evaporated, and the crude product was then separated by silica gel column chromatography eluting with hexane: dichloromethane=40:1 (v: v) to obtain polyfluorinated nanographene material C 80 H 6 F 30 The yield was 24%. C (C) 80 H 6 F 30 : 13 C{ 19 F}NMR(CDCl 3 ,25℃,125MHz)δ151.305-111.000(80C)；HRMS(MALDI-TOF-MS):C 80 H 6 F 30 [M · ] + Theoretical 1536.001 and detected 1535.592.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. An edge fluorinated nanographene material, characterized in that: the edge fluorinated nano graphene material takes nano graphene as an inner core, hydrogen atoms at the edge of the inner core are replaced by a certain number of fluorine atoms, and the number of the replaced fluorine atoms is 10-30; the chemical structural formula of the edge fluorinated nano graphene material is as follows:
wherein R is 1 And R is 2 When the fluorine atoms and the hydrogen atoms are respectively adopted, the molecular formula of the edge fluorinated nano graphene material is C 80 H 20 F 10 ；R 1 And R is 2 When the fluorine atoms are hydrogen atoms and fluorine atoms respectively, the molecular formula of the edge fluorinated nano graphene material is C 80 H 10 F 20 ；
When R is 1 And R is 2 When the two are fluorine atoms, the bonding modes of the edge fluorinated nano graphene material are respectively complete cyclization and incomplete cyclization, wherein when the two are completely cyclized, a bond is formed at a dotted line, and the molecular formula of the edge fluorinated nano graphene material is C 80 F 30 The method comprises the steps of carrying out a first treatment on the surface of the When the cyclisation is incomplete, no bond is formed at the dotted line, and the molecular formula of the edge fluorinated nano graphene material is C 80 H 6 F 30 。
2. An edge-fluorinated nanographene material according to claim 1, characterized in that: the inner core is all six-membered rings or contains defects of non-six-membered rings, wherein the non-six-membered rings are five-membered rings, seven-membered rings or eight-membered rings; when all the cores are six-membered rings, the whole space structure of the inner core is a plane; when the core contains non-six-membered ring defects, the whole space structure of the core is bent, and the structural fragment comprises any one of the following components:
3. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges replace 10 fluorine atoms altogether, R 1 Is a fluorine atom, R 2 Is a hydrogen atom, namely the molecular formula of the edge fluorinated nano graphene material is C 80 H 20 F 10 To be converted intoThe chemical structural formula is as follows:
4. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges are substituted with 30 fluorine atoms altogether, and the benzene substituent is completely cyclized, R 1 And R is 2 Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C 80 F 30 The chemical structural formula is as follows:
5. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges are substituted with 30 fluorine atoms altogether, and the benzene substituent is incompletely cyclized, R 1 And R is 2 Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C 80 H 6 F 30 The chemical structural formula is as follows:
6. a method for preparing the edge fluorinated nano graphene material according to claim 3, comprising the following steps:
s1, realizing the coupling of ten-weight Suzuki-Miyaura under the action of a palladium catalyst by using decachlorocycloalkene and 4-fluorobenzeneboronic acid to obtain ten (4-fluorophenyl) cycloalkene;
s2, passing the ten (4-fluorophenyl) endocyclic alkene in the step S1Carrying out intramolecular dehydrocyclization reaction by Scholl reaction, purifying the mixture by RP-HPLC to obtain the edge decafluoro-substituted edge fluorinated nano graphene material C 80 H 20 F 10 。
7. A method for preparing the edge fluorinated nano graphene material according to claim 4, comprising the following steps:
s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;
s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through RP-HPLC to obtain the edge perfluorinated completely cyclized edge fluorinated nano graphene material C 80 F 30 。
8. A method for preparing the edge fluorinated nano graphene material according to claim 5, comprising the following steps:
s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;
s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through silica gel column chromatography to obtain the edge polyfluoro-substituted incompletely cyclized edge fluorinated nano graphene material C 80 H 6 F 30 。
9. A method for preparing an edge fluorinated nanographene material according to any one of claims 6 to 8, wherein: the alkali adopted in the Suzuki-Miyaura coupling reaction is potassium phosphate; the organic solvent adopted in the Suzuki-Miyaura coupling reaction is toluene; the oxidant used in the Scholl reaction is 2, 3-dichloro-5, 6-dicyano-p-benzoquinone; the organic acid used in the Scholl reaction is trifluoromethanesulfonic acid; the organic solvent used in the Scholl reaction is methylene dichloride.
10. Use of the edge-fluorinated nanographene material according to claim 1, characterized in that: the edge fluorinated nano graphene material is applied to an organic field effect transistor, an organic light emitting diode and an organic photovoltaic cell as an n-type semiconductor; the edge fluorinated nano graphene material is used as a heat-resistant material and is suitable for a lubricant additive in high-temperature, high-speed and high-pressure environments; the edge fluorinated nano graphene material is suitable for biological imaging and biomedicine as a biological friendly material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311591092.0A CN117509629B (en) | 2023-11-27 | 2023-11-27 | Edge fluorinated nano graphene material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311591092.0A CN117509629B (en) | 2023-11-27 | 2023-11-27 | Edge fluorinated nano graphene material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117509629A true CN117509629A (en) | 2024-02-06 |
| CN117509629B CN117509629B (en) | 2024-10-22 |
Family
ID=89762431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311591092.0A Active CN117509629B (en) | 2023-11-27 | 2023-11-27 | Edge fluorinated nano graphene material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117509629B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130087446A1 (en) * | 2011-10-11 | 2013-04-11 | Aruna Zhamu | One-step production of graphene materials |
| CN104114489A (en) * | 2011-12-20 | 2014-10-22 | 巴斯夫欧洲公司 | Polymeric precursors for producing graphene nanoribbons and methods for preparing them |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
-
2023
- 2023-11-27 CN CN202311591092.0A patent/CN117509629B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130087446A1 (en) * | 2011-10-11 | 2013-04-11 | Aruna Zhamu | One-step production of graphene materials |
| CN104114489A (en) * | 2011-12-20 | 2014-10-22 | 巴斯夫欧洲公司 | Polymeric precursors for producing graphene nanoribbons and methods for preparing them |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117509629B (en) | 2024-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI435888B (en) | Fullerene derivatives based on fullerene derivatives and fullerene polymers and their manufacturing methods | |
| US8987538B2 (en) | Carbon nanohoops and methods of making | |
| CN109593095B (en) | X-type hetero-condensed perylene aromatic hydrocarbon double-spiro-alkene functional molecular material and preparation and application thereof | |
| Jancarik et al. | A practical general method for the preparation of long acenes | |
| CN112480050B (en) | Synthesis method of fullerene spiro-derivative | |
| CN117509629B (en) | Edge fluorinated nano graphene material and preparation method and application thereof | |
| JP2023535330A (en) | Method for producing deuterated aromatic compounds and deuterated reaction composition | |
| CN114891188B (en) | Conjugated organic metal polymer containing nitroxide free radical and ferrocene group, preparation method and application thereof, and composite thermoelectric film | |
| CN114133385B (en) | Hole transport material with carbazole as core and thiophene or phenoxazine as end group, and synthesis method and application thereof | |
| CN114349609B (en) | Synthesis method of hexabenzocoronene dimer | |
| Dutta et al. | Synthesis and self-assembly of triphenylene-containing conjugated macrocycles | |
| CN111793065B (en) | Spirocyclic aromatic organic conjugated micromolecular thermoelectric material and preparation and application thereof | |
| KR101406009B1 (en) | Fullerene derivatives and preparation thereof | |
| CN109786542B (en) | Porphyrin/carbon nanotube composite thermoelectric material and preparation method thereof | |
| Shen et al. | Metal-encapsulation induces a highly regioselective Bingel–Hirsch reaction of the labile Y@ C s (6)-C 82 | |
| JP2020196682A (en) | Curved aromatic compound and method for producing the same | |
| CN115093412B (en) | Organic thermoelectric functional material based on end-group electron-withdrawing base benzene ring derivative | |
| CN115873016B (en) | Condensed ring organic small molecule and preparation method and application thereof | |
| Peng et al. | An aza-Diels–Alder approach to nitrogen-containing tetrabenzoacene derivatives | |
| Yang | Synthesis of Novel Polydiacetylenes Towards Topochemical Polymerization | |
| CN107815308B (en) | Bipolar blue light material based on carbazole and anthracene coupling and preparation method thereof | |
| KR101855085B1 (en) | Selenium-containing organic semiconductor compound and producing method of the same | |
| Itami et al. | Perfluorocycloparaphenylenes: Fully fluorinated carbon nanorings by Ni-mediated one-pot synthesis | |
| US9701596B2 (en) | Synthesis of polycyclic aromatic hydrocarbons | |
| CN116284081A (en) | Perylene boron-nitrogen doped condensed ring aromatic hydrocarbon, and synthetic method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |